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Characterization of two types of intermolecular interactions on halogen monoxide monohydrates
Author(s) -
Gálvez Oscar,
Gómez Pedro C.,
Pacios Luis F.
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21260
Subject(s) - intermolecular force , chemistry , halogen bond , halogen , redistribution (election) , electron density , computational chemistry , hydrogen bond , electron localization function , electron transfer , ab initio , density functional theory , electron , photochemistry , molecule , organic chemistry , political science , alkyl , physics , quantum mechanics , politics , law
Monohydrates of halogen monoxides ClO·H 2 O and BrO·H 2 O have been studied by means of DFT (B3LYP) and ab initio (MP2) correlated calculations with aug‐cc‐pVnZ basis sets ranging from triple‐ up to quintuple‐ζ. These complexes might be formed in the troposphere and stratosphere and participate in chemical reactions involved in ozone depletion. Two stable structures are found that differ in the intermolecular interaction which takes place, namely: conventional XO…HOH hydrogen bond and OX…OH 2 halogen bond. We demonstrate that both types of interactions participate in the formation of these complexes yet all the computational methods tested predict a slightly greater stability for the latter OX…O link. Both intermolecular interactions are characterized upon analyzing electron density distribution, charge transfer effects, and electron localization domains. These analyses reveal the central role played by electron redistribution. Because of this, the greater spatial extent of the electron density in Cl or Br as compared to H could be the main cause to yield a slightly greater stability for the OX…O halogen bond with respect to the O…HO hydrogen bond. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009